Art of preparing iron-albuminous compounds containing phosphorus.



an earns am FRITZ ZUCKMAYER, OF ELBEBFELD, GERMANY, ASSIGNOB TO DIE. WALTHER WOLFF AND CQMPANY, GES'ELLSCHAFT MIT BESCHBANKTER HAFTUNG, OF ELBERFELD GERMANY, A COMPANY.

ART OF PREPARING IBONAIIBUMINOUS COMPOUNDS CONTAINING PHOSPHORUS.

t ,ll27,968.

Specification. of Letters Patent.

Patent-ed May 28,1912.

No Drawing. Original application filed June 30, 1910, Serial No. 569,703. Divided and this application filed April 15, 1911- To all whom it may concern v Be it known that l, Fnrrz ZUCKMAYER, a citizen of the German Empire, residing at Elberfeld, Kingdom of Prussia. Empire of Germany, have invented certain new and useful Improvements in the Art of Preparing 'l'roaAlbuminous Compounds Containing Phosphorus; and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

This invention relates to albuminous substances containing iron and phosphorus and the manufacture of the same.

' having these characteristics, can be readily obtained, if an iron salt and mctaphosphoric acid are caused to react on an albuminous substance of animal or of vegetable origin, or upon a halogen derivative of such albuminous substance. The new compounds so obtained are ,iro'n-albuminous compounds rich in phosphorus, having acid reaction and forming salts with bases. Of these salts the alkali-salts are soluble. while the earthyalkali salts and the heavy metal salts thereof are soluble with difiiculty or insoluble.

In carrying out my invention I may em-' ploy albummous substances of animal or vegetable orlgln in crude orrefined condition, including their decomposition products such as albumoses and peptones, which are, for the purposes of this invention, to be'considered as equivalents and which are included in the term albuminous substances. I also include under this term the halogen derivatives of all of the above,

which are also to be considered as equivaiems of the same for the P I ses of this\ liyention.

Serial No. 521,234. 1

The metaphosphoric acid employed in carrying out my invention may be in the form of the vitreous metaphosphoric acid of the trade, or it may be employed in'the form of an alkali salt, earthy alfal' salt, or iron salt of the said acid, or it may be employed in its nascent condition due to the reaction of water on phosphorus-pentoxid. All'these forms are included in the term metaphosphoric acid as employed in the claims.

In my applicatiomSeri-a'l Number 569,703, filed on June 30th, 1910, of which this ap' plication is a divisional application, I have claimed this invention generically. Specifically the present improvement isdistinguished from that covered, in said application by the :order in which the metaphos- .phoric acidradical and the iron are caused to act on the albuminous substance. From another point of view the present improvementis specifically distinguished from the invention specifically claimed in said parent application by the fact that under my said present invention a halogenated albuminous compound is acted on by the said reagents and, moreover, that the said presentinvention comprises as a product a halogen-iron albuminous compound whose properties are defined below.

The iron albuminous compounds rich in phosphorus, .and which contain also a hal'oid,maybe obtained either by the reaction of metaphosphoric acid and an iron compound on a halogen derivative of an albuminous compound, or byhalogenizing, according to known methods, a halogen-free ferro-allmminous compound containing phosphorus obtained according to this invention.

In carrying out this invention the starting materials are combined in relative quan- The new compounds may be separated and obtained ready for use by precipitating them from their alkaline solutions by the addition of acids.

The new haloid iron-phosphorus albuminous compounds obtained by my new process have the following properties.

' They are soluble in dilute alkalis or dilute solutions of alkali-carbonates, forming with these bases soluble salts. These salts are precipitated from such solutions by adding thereto alcohol. From the solutions in alkalis the new compounds are precipitated by salts of the earthy alkalis in the form of liflicultly soluble salts of the earthy allkali-metals. Similarly, when adding a salt of a heavy metal to a solution of an alkali salt of the new'compound, the compound of. the new albuminous body with the corresponding heavy metal is precipitated.

A very important property of the new compounds is that they are insoluble in the gastric juices, and that they are not digested by pepsin combined with hydrochloric acid, and that, on the contrary, they are readily dissolved by the alkaline intestinal liquids or juices. When acting on these new haloid iron-phosphorus albuminous compounds with pepsin combined with hydrochloric a 'd. rhalogen is split off. This property, in cor motion with its insolubility or indigestibility in pepsin combined with hydrochloric acid, distinguishes the new haloid ferro-albuminous compound from the ordinary haloid albumins, such, for example, as

iodo-casein or casein iodid, which dissolves in pepsin-hydrochloric acid after a very brief time, the iodin being split ofi in ionized form.

In water and organic solvents the new compounds are insoluble. hen dissolving the new compounds through the intervention of sodium carbonate (soda), the new compounds give rise to a green color upon adding a solution of ammonium sulfid. A precipitate is formed from such solution only after the same has been allowed to stand for many hours. Phosphoric acid can be detected in the new products only by decomposing the same with acids or alkalis. or by incinerating the same.

The new compounds may be obtained with varying percentages of iron and phosphorus. according to the relative quantities of the component substances employed in preparing the same. Thecontent of iron to be obtained is about 15%, that of phosphoric acid 'anhydrid (P 0 about 20%.

By reason of the above detailed properties,

these new compounds contain iron and phosphoric 'acid in a form very favorable to 'ready assimilation by the organism and which will=not tend to derange the stomach. They are, therefore, to be employed for therapeutic I purposes and as remedies for anemia, chlorosis and other diseases and disorders olv alimentatiointhe dose being about from 2 to? grams daily for adults and half the quantity. for children.

In' order to fully disclose my invention I will describe in detail a number of examples embodying what I consider the best manner of carrying the same into efi'ect.

Example 1: To a solution of 10 kilograms of casein in 300 liters of water and 2 kilograms of soda lye (NaHo) oi. 558 Ba-uni are added 2 kilograms of *metaphosphoric acid of the trade dissolved in water, and the whole is stirred to form an intimate m xture. To this mixture there are then added I "iron albuminous compound contains about 8% of iron, 12% of phosphoric acid. an hydr'ld (P 0 and 11.8% nitrogen.

Example 2: 3 kilograms of vitreous plies- :1

phoric acid dissolved in 30 liters of with i, are added to a solution of 10 kilograms or" the white of chicken eggs in 300 liters of water. A white precipitate is thereby formed. Thcreupon 10 liters of a 50% solution of iron chlorid are added to the whole and the mixture so formedis then rendered weakly alkaline by adding dilute alkali solution. Thereby the' whole caused to form a solution from which a new compound according to this invention is precipitated by means' of acid. The new body is isolated by filtering and washing with water and is then dried. It contain-x about 11% of iron, 19% phosphoric acid u anhydrid (P 0 and 9.5% nitrogen.

Example 3: 6 kilograms of protalbumose from casein are dissolved in 200 liters water and tothis solution is added a. solution of 2 kilograms of the metaphosphoric acid of trade in 30 liters of water. A white precipitate is thus formed. To this mixture there are then added 10 liters of a 50% solution of chlorid of iron and thereupon a weak alkaline reaction is eii'ected by the addition of dilute solution of ammonia. A solution is thereby obtained, and from this solution a new iron-albuminous compound is separated by the addition of acid. As in the former examples, the new product is isolated by filtering, washing with water, and drying. .On analyzing the same it is found that it contains about 16% of iron, 21% of phosphoric acid anhydrid (P 0 and 9% nitrogen.

Example 4: 4 kilograms of iodo-casein or casein iodid are dissolver in 150 liters of water to ether with a small quantity of ammoniasodution and thereupon there is added thereto a'solution of 0.8 kilograms of commercial metaphosphoric acid in 4 liters of water, this addition resulting in a yellowish precipitate. To the whole are now added 6 liters of. a 25% solution of iron chlorid,

whereupon the bath is heated to from il)",

iic

to 50 centigrade, and suflicient ammonia solution is added to obtain'weak alkaline reaction. A solution of the precipitate is thereby obtained. From this solution a new compound is separated by adding an acid, such, for example, as hydrochloric acid. The same is then separated and purified by filtering and washing with water until free of chlorin. It is then dried. The new prod-. uct, so obtained, contains about 9% of iron. 12% of P 0 7% of iodin, and 11.4% ol nitrogen.

Example 5: 5 kilograms of casein are digested with the proper. mixture of pepsin and hydrochloric acid and the so obtained mixture of casein-albuminoses and peptones is rendered neutral by adding thereto sufiicient soda-lye (sodium hydrate solution). It is thereupon treated with a solution of 1 kilogram of iodin in 4 liters of water and 1 kilogram of potassium iodid, the mixture being maintained at 40, centigrade, and rendered slightly alkaline by the addition thereto of a solution of sodium bicarbonate. The mixture is tested for free iodin from time to time, and when the tests show that no'more free iodin is present, there is added to the mixture a solution of 1 kilogram of vitreous metapho-sphoric acid in 5 liters of water, and thereupon 8 liters of a 25% solu tion of chlorid of iron is added wh'ile stirring. Thereupon dilute aqueous solution of ammonia is-added until the mixture gives an alkaline reaction, at which stage a solution is formed. The solution is then separated from thesmall quantity of impurities by filtration and from the filtrate or solution the new compound is precipitated by means of dilute acid. The precipitate is then washed with water until the .wash-water is found to be free of halogen and itis then dried. The new compound so obtained contains about 10% of iron, 11% of P 0 6.5% iodin, and 11% of nitrogen.

Example 6: kilograms of dried white of chicken egg are dissolved in 100 liters of water, and to this solution there is slowly added, while well stirring. a solution of 1.5 kilograms of bromin in 75 liters of water. The mixturithen rendered weakly alkaline with dilute aqueous solution of ammonia. By virtue of this addition a complete solution is formed. Thereupon a solution of 1 kilogram of commercial metaphosphoric acid in 5 liters of-water is added while stirring, and then 8 liters of a 25% solution of chlorid of iron is added, the mixlure being then treated with ammonia solution until alkaline reaction occurs, and a solu ion takes place. The resultant solution 1? then filtered to'remove impurities and to .ll'e filtrate or purified solution there is then added dilute hydrochloric acid to precipitate the new compound. The precipitate is separated by filtration, thoroughly washed With water, and dried. The new product contains about 11% of iron, 13% of P 0 2.7% of bromin and 11% of nitrogen.

Example 7: 5 kilograms of the new compound resulting from the. process described under Example 1 are dissolved in 150 liters of water, to which is added the necessary quantity of sodium bicarbonate to form the solution. The solution thus formed is then treatedwith a solution of 1 kilogram of iodin in 1 kilogram of potassium iodid and 5 liters of water, the Whole bein maintained slightly alkaline by the addition of a sodium bicarbonate solution. As soon as nomore free iodin can be detected, the

solution is filtered and the new compound is separated from the filtrate by the addi- 'tion of dilute acid, such as dilute HCl. The

precipitate is isolated by filtration; itis washed thoroughly with water and dried. The new compound contains about 6.4% of iron, 8.2% of phosphoric acid anhydrid (P 0 7.7% of iodin, and 11.5% of nitrogen.

From the above examples it will be seen that lron albuminous compounds rich in phosphorus are obtained in allcases,whether these albuminous compounds are free ofhalogen or contain halogen.

While I have in Examples 1, 2 and 3 described my invention as applied to.the production of halogen free iron-albuminous compounds containing phosphorus in illustration of my invention generically considered, I do not herein claim the same specifically, since the same have been thus claimed in my aforesaid application Serial No. 569703. For the same reason I do not herein 'claim specifically the process in which the iron is caused to react upon the albuminous compound before the metaphosphoric acid radical.

What I claim and desire to secure by Letters Patent isz- I. The process of making iron-albuminous compounds containing phosphorus; which consists in causing a compound containing the metaphosphoric acid radical to react on the metaphosphoric acid radical to react on a halogenated albumin, and then causing an iron compound to react on the resultant product.

4. The process of making iron-albuminous compounds containing phosphorus, which consists in causing a soluble-iron compound and a compound containingthe metaphos phoric acid radical to react I on a halogenalbunnnous compound.

5. The process of making iron-albuminous compounds containing phosphorus, which consists in causing a soluble iron compound and metaphosphonc acid to react on halogen-albuminous compound.

a halogen-albuminous compound, and then causing an iron compound to react on the same.

7.- As a new composition of matter, a

halogen iron-albuminous compound containv ing phosphorus and having the following" properties it is soluble in dilute ime -01 dilute solutions of alkali czirbonete, insoluble in water and organic solvents; when dissolving it with aid of'sodium carbon ete It gives rise to a green color on addingainmoniuin sulfid; it is insoluble in 6 sin combined with hydrochloric phoricacid can be detected i "P 35' therein only upon decomposition or mcmeratwn; when" reacting on the same with pef sin combined with hydrochloric acid no he, og 'en' is Iihfer- In testiminiy whereof I. hereunto, my

g iuue the resence of two Witnesses.

FRI'l-Zi- UCKMAYER [14,51 Witnesses M ALFRED HZin EL, 

